Bowker M., Davies P.R. (Eds.) Scanning Tunneling Microscopy in Surface Science, Nanoscience and Catalysis

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Scanning Tunneling

Microscopy

in Surface Science,

Nanoscience

and Catalysis

Michael Bowker and Philip R. Davies,

Editors

WILEY-VCH Verlag GmbH

Scanning Tunneling Microscopy

in Surface Science, Nanoscience

and Catalysis

Edited by

Michael Bowker and Philip R. Davies

Scanning Tunneling Microscopy

in Surface Science, Nanoscience

and Catalysis

Edited by

Michael Bowker and Philip R. Davies

Further Reading

K.W. Kolasinski

Surface Science

Foundations of Catalysis

and Nanoscience

2008

ISBN: 978-0-470-03304-3

D.G. Brandon, W.D. Kaplan

Microstructural

Characterization of Materials

2008

ISBN: 978-0-470-02784-4

J.W. Niemantsverdriet

Spectroscopy in Catalysis

An Introduction

2007

ISBN: 978-3-527-31651-9

B.P. Jena, J.K.H. Hoerber (Eds.)

Force Microscopy

Applications in Biology and Medicine

2006

ISBN: 978-0-471-39628-4

M. Prutton, M. El Gomati (Eds.)

Scanning Auger Electron

Microscopy

2006

ISBN: 978-0-470-86677-1

D.K. Schroder

Semiconductor Material and

Device Characterization

2006

ISBN: 978-0-471-73906-7

Scanning Tunneling Microscopy

in Surface Science, Nanoscience

and Catalysis

Edited by

Michael Bowker and Philip R. Davies

The Editors

Prof. Michael Bowker

Cardiff University

Wolfson Nanoscience Lab and

Cardiff Catalysis Institute

School of Chemistry

Cardiff, CF10 3AT

United Kingdom

Dr. Philip R. Davies

Cardiff University

Wolfson Nanoscience Lab and

Cardiff Catalysis Institute

School of Chemistry

Cardiff, CF10 3AT

United Kingdom

Cover illustration

The STM images being past of the front cover picture

have been kindly provided by the group of D. Wayne

Goodman (authos of Chapter 3).

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Contents

Preface IX

List of Contributors XIII

1 Chirality at Metal Surfaces 1

Chris J. Baddeley and Neville V. Richardson

1.1 Introduction 1

1.1.1 Deﬁnition of Chirality 1

1.1.2 Nomenclature of Chirality: The (R),(S) Convention 2

1.2 Surface Chirality Following Molecular Adsorption 4

1.2.1 Achiral Molecules on Achiral Surfaces 4

1.2.2 Lattice Matching 8

1.2.3 Chiral Molecules on Achiral Surfaces 12

1.2.4 Chiral Molecules on Chiral Surfaces 15

1.2.5 Chiral Etching 16

1.3 Chiral Ampliﬁcation and Recognition 19

1.3.1 Chiral Ampliﬁcation in Two Dimensions 19

1.3.2 Chiral Switching 20

1.3.3 Chiral Recognition 21

1.3.4 Prochiral Molecules Interacting with Chiral Surfaces 24

1.4 Conclusions 25

References 26

2 The Template Route to Nanostructured Model Catalysts 29

Conrad Becker and Klaus Wandelt

2.1 Introduction 29

2.2 Surfaces as Two-Dimensional Templates 31

2.3 STM Imaging of Oxide Films 34

2.4 STM Imaging of Metal Particles on Oxide Films 39

2.5 Template-Controlled Growth of Model Catalysts 44

2.5.1 Oxides as Templates 44

2.5.2 Modiﬁed Templates 50

2.6 Conclusions 51

References 52

3 In Situ STM Studies of Model Catalysts 55

Fan Yang and D. Wayne Goodman

3.1 Introduction 55

3.2 Instrumentation 56

3.3 Visualizing the Pathway of Catalytic Reactions 59

3.3.1 Imaging of Adsorbates and Reaction Intermediates 59

3.3.2 Imaging Chemisorption on Metals 61

3.3.3 Determining the Sites for Chemisorption on Oxide Surfaces 64

3.3.4 Visualizing Reaction Intermediates and the Mechanism

of Hydrogen Oxidation 71

3.3.5 Measuring the Reaction Kinetics of CO Oxidation 73

3.4 Metal Surfaces at High Pressures 81

3.5 In Situ Studies of Supported Model Catalysts 85

3.5.1 Monitoring the Growth Kinetics of Supported Metal Catalysts 85

3.5.2 Studies of the SMSI Effect 88

3.5.3 Sintering Kinetics of Supported Au Clusters 89

3.6 Outlook 91

References 92

4 Theory of Scanning Tunneling Microscopy and Applications

in Catalysis 97

Gilberto Teobaldi, Haiping Lin, and Werner Hofer

4.1 Catalysis and Scanning Tunneling Microscopy 97

4.2 Image Formation in an STM 98

4.3 Simulating Tunneling Currents 99

4.4 Simulating Chemical Reactivity 100

4.5 Catalytic Water Production 101

4.5.1 TiO

: A Catalytic Model System 106

4.6 Outlook 115

References 116

5 Characterization and Modification of Electrode Surfaces

by In Situ STM 119

Dieter M. Kolb and Felice C. Simeone

5.1 Introduction 119

5.2 In Situ STM: Principle, Technical Realization and Limitations 120

5.2.1 Principle Considerations for In Situ Operation 120

5.2.2 Technical Realization 124

5.2.2.1 Tip Preparation and Isolation 124

5.2.2.2 Electrochemical Cell 126

5.2.2.3 Vibration Damping 127

VI Contents

5.2.3 Limitations 127

5.3 Imaging Single-Crystal Surfaces of Catalytically Relevant

Systems 128

5.3.1 Preparation and Imaging of Metal Single-Crystal Surfaces 128

5.3.2 Bimetallic Surfaces 130

5.4 Strategies for Nanostructuring Surfaces 132

5.4.1 Oxidation–Reduction Cycles for Roughening and Faceting

Surfaces 132

5.4.2 Surface Modiﬁcation by an STM: An Overview 134

5.4.3 Metal Nanocluster Deposition via Jump-to-Contact 139

References 144

6 STM Imaging of Oxide Nanolayer Model Systems 147

Falko P. Netzer and Svetlozar Surnev

6.1 Introduction 147

6.2 Experimental Aspects and Technical Developments 149

6.3 Case Studies: Selected Oxide– Metal Systems 152

6.3.1 Alumina Nanolayers on NiAl Alloys 152

6.3.2 Titanium Oxide Nanolayers 155

6.3.3 Vanadium Oxide Nanolayers 159

6.3.4 Iron Oxides on Pt(1 1 1) 169

6.3.5 Nickel Oxide Nanolayers 173

6.3.6 Ceria Nanolayers on Metal Surfaces 177

6.4 Synopsis and Outlook 182

References 183

7 Surface Mobility of Atoms and Molecules Studied with

High-Pressure Scanning Tunneling Microscopy 189

Gabor A. Somorjai, Feng Tao, and Derek Butcher

7.1 Introduction 189

7.2 Characterization of Surface Mobility of Molecules and Atoms 189

7.3 High-Pressure STM Technique and Instrumentation 191

7.4 Mobility and Flexibility of Catalyst Surfaces at High-Pressure

High-Temperature Reaction Conditions 197

7.5 Adsorbate Mobility During Catalytic Reactions 206

7.5.1 Ethylene Hydrogenation on Pt(1 1 1) 207

7.5.2 Hydrogenation of C

Cyclic Hydrocarbons on Pt(1 1 1) 209

7.5.3 CO/NO Coadsorption on Rh(1 1 1) 213

7.6 Summary 216

References 216

Contents VII